US5614603A - Thermosetting silicone resins - Google Patents
Thermosetting silicone resins Download PDFInfo
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- US5614603A US5614603A US08/593,318 US59331896A US5614603A US 5614603 A US5614603 A US 5614603A US 59331896 A US59331896 A US 59331896A US 5614603 A US5614603 A US 5614603A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
Definitions
- thermosetting silicone resins that provide highly heat-resistant and optically transparent cured products with excellent hardness.
- This invention also relates to a method for curing these thermosetting silicone resins.
- Silicone resins are polymers with a three-dimensional structure. They are obtained by the hydrolysis and condensation of organosilane compounds. A substantial amount of information exists on the preparation and properties of silicone resins, on methods for curing these resins and on the physical properties of their cured products (Silicone Handbook, edited by Kunio Itoh, Nikkan Kogyo Shinbunsha, page 468; Chemistry and Technology of Silicones, 2nd Edition, p. 409, Walter Noll, Academic Press, Inc. (London) Ltd., 1968).
- Silicone resins generally include DT resins, polysilsesquioxanes, and in some cases, MQ resins.
- DT resins are prepared by the cohydrolysis of difunctional and trifunctional hydrolyzable silane compounds.
- Difunctional hydrolyzable silane compounds possess 2 hydrolyzable functional groups and produce the siloxane unit known as the D unit ((--O) 2 SiR 2 ).
- Trifunctional hydrolyzable silane compounds possess 3 hydrolyzable functional groups and produce the siloxane unit known as the T unit ((--O) 3 SiR).
- Polysilsesquioxanes are produced by the hydrolysis of only trifunctional hydrolyzable silane compounds.
- MQ resins are produced by the cohydrolysis of monofunctional hydrolyzable silane compounds and tetrafunctional silane compounds.
- Monofunctional hydrolyzable silane compounds possess 1 hydrolyzable functional group and produce the siloxane unit known as the M unit (--OSiR 3 ).
- Tetrafunctional hydrolyzable silane compounds such as silicon tetrachloride, in which all the functional groups are hydrolyzable, possess 4 hydrolyzable functional groups and produce the siloxane unit known as the Q unit (Si(O--) 4 ).
- Q unit Si(O--) 4
- these silicone resins are used as heat-resistant coatings, protective coatings, electrical-insulating coatings, and so forth. These applications require that the uncured resin exhibit a good moldability and that the cured product exhibit heat resistance, hardness, etc.
- the by-product-free curing reactions include (1) polymerization of silicone-bonded reactive organofunctional groups such as epoxy, methacryloxy, etc., and (2) hydrosilylation of an SiH and an Si-alkenyl (e.g., vinyl, allyl, etc).
- silicone-bonded reactive organofunctional groups such as epoxy, methacryloxy, etc.
- hydrosilylation of an SiH and an Si-alkenyl e.g., vinyl, allyl, etc.
- each of these reactions produce a by-product, e.g., water, alcohol, oxime, amide, acetic acid, and acetone.
- a by-product e.g., water, alcohol, oxime, amide, acetic acid, and acetone.
- thermostable siloxane bonds by moisture-mediated curing reactions as commonly used for curing silicone resins (dehydration, alcohol elimination, oxime elimination, acetic acid elimination, acetone elimination, amide elimination, etc.), it is difficult to induce the formation of a thick, hard film. Moreover, a large weight loss occurs during cure. These factors cause substantial problems in terms of volume loss, warping, cracking, and so forth. Moreover, the fabrication of thick, hard monoliths is encumbered by the development of voids, cracks and dimensional instability in the cured material in association with vaporization of volatile by-products formed by the curing reaction.
- Resins containing large amounts of Q unit are used in applications where the hardness of the cured product is critical (e.g., in polysilsesquioxanes or DT resins).
- the uncrosslinked resin to gel as the Q unit content increases.
- the resin solubility, viscosity and processability also deteriorate.
- crosslink density is reduced still further by the presence of large amounts of the triarylsiloxy group, which is a bulky end group. It is noted that Wu did make reference to curing the polymers through hydrosilylation using the hydrogen atom on the T unit of this siloxane. Again, however, crosslinking based on the hydrosilylation reaction produces Si--C bond crosslinks, which precludes the preparation of a highly thermostable cured material.
- the present invention takes as its object a solution to the problems described above for the prior art through the introduction of a highly spin-coatable thermosetting resin that provides an optically transparent and highly heat-resistant cured product having an excellent hardness.
- the inventors carried out intensive and extensive investigations into increasing the crosslink density of the cured product without impairing the solubility, solution viscosity, spin-coatability, etc., of the uncrosslinked resin; suppressing the weight loss and volume shrinkage that accompanies curing; and obtaining a highly thermostable cured product.
- a silicone resin containing both the diphenylsiloxane unit and hydrogensilsesquioxane unit can satisfy the above requirements.
- the present invention relates to a silicone resin.
- the resin comprises a silicone polymer having the general formula (Ph 2 SiO) a (HSiO 3/2 ) b (R 1 SiO 3/2 ) c .
- each R 1 independently represents C 1 to C 18 hydrocarbon groups which may contain at least 1 atom selected from the group consisting of oxygen, nitrogen, chlorine, fluorine, and silicon.
- the Ph in the formula represents a phenyl group.
- the other bond of the O in the formula may attach to silicon to form a siloxane bond or may attach to a hydrogen atom to form silanol.
- the average degree of polymerization of the polymer molecule i.e., a+b+c
- the average proportions of the monomer units fall within the following ranges:
- the present invention also relates to method for the preparation of the above silicone resin.
- the method comprises adding diphenylsilanediol to either (1) HSiX 3 or (2) the mixture of HSiX 3 and R 1 SiX 3 and then hydrolyzing the silicone resin at temperatures not exceeding 100° C.
- each X independently denotes a hydrolyzable group selected from the chlorine atom and bromine atom and R 1 is defined as above,
- the present invention also relates to a thermosetting polyorganosiloxane composition.
- the composition comprises
- the catalytic component is present in the mixture at 0.01 to 10 weight % based on the silicone resin when it is a basic compound or a divalent or tetravalent tin compound.
- the catalytic component is present in the mixture at 0.00001 to 1 weight % based on the silicone resin when it is palladium metal, platinum metal, a palladium compound, or a platinum compound.
- the present invention also relates to a method for curing the above silicone resin.
- The;method comprises heating the silicone resin at 200° C. to 500° C.
- the method comprises heating the above silicone resin and catalyst composition at temperatures not exceeding 500° C.
- the present invention makes possible the fabrication of highly heat-resistant, transparent cured products that have excellent hardness. This is accomplished by the use of a very spin-coatable silicone polymer molecule that does not evolve large amounts of volatiles during its cure.
- the essential starting components for this silicone polymer molecule are diphenylsilanediol and trihalosilane, and the resultant resin contains diphenylsiloxane (Ph 2 SiO 2/2 ) and hydrogensilsesquioxane (HSiO 3/2 ) as its essential components. More specifically, the hydrogensilsesquioxane unit (HSiO 3/2 ) in the polymer molecule reacts with the hydroxyl group (OH)--thereby forming the silicon-oxygen bond (Si--O) and a hydrogen molecule (H 2 )--and also forms the silicon-oxygen bond (Si--O) through its oxidation when heated in the presence of oxygen. Crosslinking and curing of the silicone polymer molecule therefore proceeds through the very thermostable siloxane bond, which means that this curable silicone polymer molecule can be used to fabricate cured silicone products that are highly heat resistant.
- each R 1 independently represents C 1 to C 18 hydrocarbon groups, which may contain at least 1 atom selected from oxygen, nitrogen, chlorine, fluorine, and silicon. Ph represents the phenyl group.
- the other bond of the O which is the divalent oxygen atom bonded to silicon in general formula (1), may at h to silicon to form a siloxane bond or may attach to a hydrogen atom to form silanol.
- the average degree of polymerization of the polymer molecule, i.e., a+b+c, is 6 to 1,000.
- the average proportions of monomer units in the polymer molecule fall within the following ranges:
- the molecular weight of the product declines when a in the composition of the polymer molecule deviates substantially from the range specified above.
- b/(b+c) falls below the above-specified range, the Q unit content in the cured product will be reduced and the hardness of the cured product will decline.
- the second embodiment of the present invention relates to a method for the preparation of the above silicone resin.
- the method comprises the hydrolysis--at temperatures not exceeding 100° C. --of the silicone resin obtained by the addition of diphenylsilanediol to the silane compound or compounds that generate the T component of subject silicone resin, i.e., to HSiX 3 or the mixture of HSiX 3 and R 1 SiX 3 (R 1 is defined as above and each X independently represents a hydrolyzable group selected from chlorine and bromine).
- An acid acceptor is preferably used in this reaction at fewer gram-equivalents than the total for X.
- the acid acceptor may be preliminarily added to the HSiX 3 or HSiX 3 /R 1 SiX 3 mixture or may be added together with the diphenylsilanediol to the HSiX 3 or HSiX 3 /R 1 SiX 3 mixture. Since the acid acceptor often a good solvent for diphenylsilanediol, a particularly preferred technique consists of dissolving the diphenylsilanediol in the acid acceptor and adding the mixture to the HSiX 3 or HSiX 3 /R 1 SiX 3 mixture. However, adding excess acid acceptor during hydrolysis must be avoided since it makes the system alkaline.
- Acid acceptors suitable for the present purpose are exemplified by ammonia; alkylamines and aralkylamines such as methylamine, hexylamine, octylamine, aniline, benzylamine, dimethylamine, diethylamine, dihexylamine, ethylbenzylamine, trimethylamine, triethylamine, tripropylamine, and dimethylbenzylamine; and aromatic amines such as pyridine, picoline, and quinoline.
- alkylamines and aralkylamines such as methylamine, hexylamine, octylamine, aniline, benzylamine, dimethylamine, diethylamine, dihexylamine, ethylbenzylamine, trimethylamine, triethylamine, tripropylamine, and dimethylbenzylamine
- aromatic amines such as pyridine, picoline, and quinoline.
- the diphenylsilanediol be added to the HSiX 3 or HSiX 3 /R 1 SiX 3 mixture. If the materials are added in reverse, gelation of the resin is facilitated in the initial stage of synthesis due to the development of the crosslinked structure of the resin. Moreover, the secondary production of T unit-rich resin during hydrolysis is also facilitated.
- the diphenylsilanediol, HSiX 3 or HSiX 3 /R 1 SiX 3 mixture may be dissolved in organic solvent for use in this process.
- the precursors for the HSiO 3/2 and R 1 SiO 3/2 for example, HSiCl 3 and R 1 SiCl 3 , are placed in a reactor.
- silicone resin bearing hydrolyzable chloride is first synthesized by the addition of diphenylsilanediol together with acid acceptor (added at fewer mole-equivalents than the total for the silicon-bonded chlorine on the chlorosilane in the reactor). While cooling the reactor to a temperature not exceeding 50° C., the synthesis proceeds by hydrolysis of the resin with a large amount of water and then thoroughly washing the organic component thereby produced with water.
- the sequence of addition of the reagents, the reaction temperature, and the hydrolysis conditions are very important in terms of being able to run the reaction while inhibiting gelation reactions in said resin.
- the presence of the acid acceptor is not essential to the subject reaction, but its addition does accelerate the reaction.
- silane that provides the M component upon hydrolysis makes possible rational control of the molecular weight of the resin and also permits the introduction of reactive functional groups.
- Said M component-generating silane is exemplified by trimethylchlorosilane, vinyldimethylchlorosilane, dimethylchlorosilane, and triphenylchlorosilane.
- silane that provides the D component upon hydrolysis permits rational control of resin hardness and also permits the introduction of reactive functional groups.
- Said D component-generating silane is exemplified by dimethyldichlorosilane, methyldichlorosilane, vinylmethyldichlorosilane, and phenylmethyldichlorosilane.
- silane that provides the Q component upon hydrolysis such as silicon tetrachloride, permits rational regulation of resin hardness.
- the third embodiment of the present invention relates to compositions comprising the above silicone polymer molecule (1) and a catalyst for its curing reaction. More specifically, these are compositions comprising the above silicone polymer molecule and at least 1 catalytic component selected from the group consisting of basic compounds, divalent and tetravalent tin compounds, palladium, platinum, palladium compounds, and platinum compounds.
- the quantity of addition for obtaining ideal curing properties and ideal physical properties in the cured product is 0.01 to 10 weight % and more preferably 0.1 to 5 weight %, in each case based on the silicone polymer molecule.
- the suitable quantities are 0.00001 to 1 weight % and more preferably 0.00005 to 0.1 weight %, in each case based on the silicone polymer.
- the basic compounds are exemplified by ammonia, primary organic amines, secondary organic amines, tertiary organic amines, ammonium halides, quaternary ammonium hydroxides, and quaternary phosphonium hydroxides.
- the tin compounds are exemplified by the carboxylate salts of divalent tin, the alkyl and aryl compounds of divalent tin, the alkoxy compounds of divalent tin, the alkyl and aryl compounds of tetravalent tin, dialkyltin(IV) dicarboxylates, dialkyltin(IV) bis(acetylacetonate)s, and the alkoxy compounds of tetravalent tin.
- the palladium catalysts are exemplified by palladium metal, as typified by palladium black, and by the olefin complexes of palladium(II) halides.
- the platinum catalysts are exemplified by platinum metal, as typified by platinum black, as well as by chloroplatinic acid, the olefin complexes of platinum(II) halides, the phosphine complexes of platinum(II) halides, the olefin complexes of zero-valent platinum, and so forth.
- the above catalysts function as catalysts of the reaction of the hydroxyl group and SiH to produce a hydrogen molecule and the silicon-oxygen bond. As long as this reaction is not poisoned, other catalytic components such as titanium compounds may be added to composition.
- the fourth embodiment of the present invention relates to a method for curing the above silicone resin and for curing the above polyorganosiloxane/curing catalyst compositions.
- the method comprises heating the silicone resin (without curing catalyst) at temperatures of 200° C. to 500° C.
- the polyorganosiloxane/curing catalyst compositions are heated at a temperature of at least 50° C. but not exceeding 500° C.
- the time required for curing is not crucial, but in practical terms curing will be carried out for approximately several seconds to several tens of minutes at high temperatures (500° C.) and for 1 hour to several days at low temperatures. Under these conditions, curing proceeds through siloxane bond formation by dehydrogenative condensation between silanol and SiH and oxidation of SiH by atmospheric oxygen and/or hydrolysis by atmospheric moisture. Accordingly, when silanol is not present in the silicone polymer molecule, heating should be carried out in air or in the presence of oxygen or water. However, no specific restrictions need be formulated here as long as the usual concentrations of moisture and/or oxygen are present.
- the silanol in the composition undergoes a dehydrogenative condensation reaction with the SiH in the same composition, and a siloxane bond is thereby formed with the loss of a hydrogen molecule.
- this dehydrogenative condensation reaction is accompanied by siloxane bond formation through a dehydration condensation between silanols with the loss of a water molecule.
- SiH is present in excess relative to silanol, the residual SiH will react with atmospheric water or oxygen to form silanol, which will then undergo dehydrogenative condensation with another SiH to form a siloxane bond with the loss of a hydrogen molecule.
- the reaction of SiH with silanol results in only a weight loss of 2 g (hydrogen molecule) per 1 mole of siloxane bonds formed.
- the reaction between SiH groups results in the uptake of an oxygen atom and loss of a hydrogen molecule, or a weight gain of 14 g (gain due to the oxygen atom and loss of the hydrogen molecule) per 1 mole of siloxane bonds formed.
- 1 H-NMR and 29 Si ⁇ 1H ⁇ -NMR denote, respectively, proton nuclear magnetic resonance spectra and silicon-29 nuclear magnetic resonance spectra (proton decoupled) in the product property descriptions in the examples below.
- Quantitative 29 Si-NMR measurements were run with the addition of tris(acetylacetonate)chromium(III) to a deuterochloroform (CDCl 3 ) solution of the sample. The details are reported in The Analytical Chemistry of Silicones, edited by A. Lee Smith, John Wiley & Sons, Inc. (1991), page 377.
- the a:b:c ratio can be determined as the relative intensity for each functional group in the 29 Si-NMR.
- the chemical shifts in the 1 H-NMR spectra were in all cases assigned by using 7.24 ppm for the resonance position of the residual CHCl 3 in the CDCl 3 solvent.
- the chemical shifts in the 29 Si-NMR spectra were assigned by using 0 ppm for the chemical shift of silicon in a tetramethylsilane external standard (CDCl 3 solution).
- TG refers to thermal gravimetric analysis. In the examples and comparative examples, the weight change during TG was measured in air at a temperature rise of 10° C./minute, and the temperature at which the weight of the sample had declined by 10% during this measurement is reported as Td10.
- GPC refers to gel permeation chromatography.
- toluene was used as the solvent in GPC, and the molecular weight is the value based on polystyrene.
- Mn refers to the number-average molecular weight
- Mw refers to the weight-average molecular weight
- Ph is an abbreviation for phenyl
- Me is an abbreviation for methyl.
- the molecular weight determined by GPC for silicones containing the diphenylsiloxane unit and the like tends to be somewhat smaller than the actual molecular weight.
- the molecular weight afforded by GPC tends to be only slightly different from the actual molecular weight.
- Zero-valent platinum/vinylsiloxane complex sufficient to give 100 ppm platinum based on resin was added to the 20 weight % toluene solution of diphenylsiloxane-hydrogensilsesquioxane resin prepared in Example 1. This was spin-coated (1,000 rpm, 5 seconds) on a silicon wafer and dried at ambient temperature. The silicon wafer was then heated in the air for 1 hour at 400° C. to give a cured resin film. The infrared absorption spectrum of the cured film indicated complete disappearance of the Si--H group. The pencil hardness of this cured film was 3H.
- a 20 weight % toluene solution of the diphenylsiloxane-methylsilsesquioxane-hydrogensilsesquioxane resin synthesized in Example 2 was prepared. To this solution was added cyclohexylamine at 5 weight % referred to the resin. The solution was then spin-coated (1,000 rpm, 5 seconds) on a silicon wafer and dried at ambient temperature. The silicon wafer was thereafter heated in the air for 1 hour at 250° C. to give a cured resin film. The infrared absorption spectrum of the cured film indicated complete disappearance of the Si--H group. The pencil hardness of this cured film was 2H.
- a column-like sample (4 mm ⁇ 5 mm ⁇ 15 mm) was fabricated by first heating the diphenylsiloxane-methylsilsesquioxane-hydrogensilsesquioxane resin from Example 2 in a vacuum for 1 hour at 50° C. in order to eliminate the volatiles and then heating--without the addition of catalyst--for 3 hours at 400° C.
- the linear coefficient of thermal expansion measured on this sample was 120 ppm/°C.
- a 20 weight % toluene solution of the diphenylsiloxane-methylsilsesquioxane-hydrogensilsesquioxane resin synthesized in Example 2 was prepared. To this solution was added tin(II) octanoate at 1 weight % based on the resin. The solution was then spin-coated (1,000 rpm, 5 seconds) on a silicon wafer and dried at ambient temperature. The silicon wafer was thereafter heated in the air for 1 hour at 250° C. to give a cured resin film. The infrared absorption spectrum of the cured film indicated complete disappearance of the Si--H group. The pencil hardness of this cured film was 2H.
- a colorless, transparent cured resin was also obtained by casting the aforementioned solution and then thermosetting (250° C., 1 hour). This cured resin sample had a Td10 in air of 501° C.
- a 20 weight % toluene solution of the diphenylsiloxane-methylsilsesquioxane-hydrogensilsesquioxane resin synthesized in Example 2 was prepared. To this solution was added sufficient zero-valent platinum/vinylsiloxane complex to give 1,000 ppm platinum based on the resin. The solution was then spin-coated (1,000 rpm, 5 seconds) on a silicon wafer and dried at ambient temperature. The silicon wafer was thereafter heated in the air for 1 hour at 250° C. to give a cured resin film. The infrared absorption spectrum of the cured film indicated complete disappearance of the Si--H group. The pencil hardness of this cured film was 3H.
- a 20 weight % toluene solution of the diphenylsiloxane-phenylsilsesquioxane-hydrogensilsesquioxane resin synthesized in Example 3 was prepared. To this solution was added sufficient zero-valent platinum/vinylsiloxane complex to give 100 ppm platinum based on the resin. The solution was then spin-coated (1,000 rpm, 5 seconds) on a silicon wafer and dried at ambient temperature. The silicon wafer was thereafter heated in the air for 1 hour at 400° C. to give a cured resin film. The infrared absorption spectrum of the cured film indicated complete disappearance of the Si--H group. The pencil hardness of this cured film was 2H.
- the 20 weight % toluene solution of diphenylsiloxane-hydrogensilsesquioxane resin prepared in Example 1 (without catalyst addition) was spin-coated (1,000 rpm, 5 seconds) on a silicon wafer. After drying at ambient temperature, the silicon wafer was heated at 480° C. in air for 20 minutes to give a cured resin film. The infrared absorption spectrum of the cured film indicated complete disappearance of the Si--H group. The pencil hardness of this cured film was 3H.
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Applications Claiming Priority (2)
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JP7-016186 | 1995-02-02 | ||
JP01618695A JP3542185B2 (ja) | 1995-02-02 | 1995-02-02 | シリコーンレジン、これを含む組成物およびその硬化方法 |
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US5614603A true US5614603A (en) | 1997-03-25 |
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US08/593,318 Expired - Fee Related US5614603A (en) | 1995-02-02 | 1996-01-31 | Thermosetting silicone resins |
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US (1) | US5614603A (de) |
EP (1) | EP0725103B1 (de) |
JP (1) | JP3542185B2 (de) |
KR (1) | KR100359392B1 (de) |
DE (1) | DE69629405T2 (de) |
TW (1) | TW413693B (de) |
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US20040186223A1 (en) * | 2001-10-22 | 2004-09-23 | Ronald Boisvert | Etch-stop resins |
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JP4783117B2 (ja) * | 2005-10-21 | 2011-09-28 | 東レ・ダウコーニング株式会社 | シリカ系ガラス薄層付き無機質基板、その製造方法、コーテイング剤および半導体装置 |
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- 1996-01-31 DE DE69629405T patent/DE69629405T2/de not_active Expired - Fee Related
- 1996-01-31 EP EP96300675A patent/EP0725103B1/de not_active Expired - Lifetime
- 1996-02-02 KR KR1019960002499A patent/KR100359392B1/ko not_active IP Right Cessation
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US6562465B1 (en) * | 1998-04-24 | 2003-05-13 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming a silica-containing film with a low-dielectric constant and substrate coated with such a film |
US20040138399A1 (en) * | 2001-04-03 | 2004-07-15 | Mackinnon Iain Alasdair | Preparation of silicone resins |
US6924346B2 (en) | 2001-10-22 | 2005-08-02 | Dow Corning Corporation | Etch-stop resins |
US20040186223A1 (en) * | 2001-10-22 | 2004-09-23 | Ronald Boisvert | Etch-stop resins |
US7405251B2 (en) * | 2002-05-16 | 2008-07-29 | Dow Corning Corporation | Flame retardant compositions |
US20060252890A1 (en) * | 2002-05-16 | 2006-11-09 | Dow Corning Corporation | Flame retardant compositions |
WO2005037907A1 (en) * | 2003-10-07 | 2005-04-28 | Honeywell International Inc. | Coatings and hard mask compositions for integrated circuit applications, methods of production and uses thereof |
US20070022909A1 (en) * | 2003-10-07 | 2007-02-01 | Joseph Kennedy | Coatings and hard mask compositions for integrated circuit applications methods of production and uses thereof |
US8101015B2 (en) | 2003-10-07 | 2012-01-24 | Honeywell International Inc. | Coatings and hard mask compositions for integrated circuit applications methods of production and uses thereof |
US20080014335A1 (en) * | 2004-12-17 | 2008-01-17 | Peng-Fei Fu | Method for Forming Anti-Reflective Coating |
US8025927B2 (en) * | 2004-12-17 | 2011-09-27 | Dow Corning Corporation | Method for forming anti-reflective coating |
US20090117392A1 (en) * | 2005-05-27 | 2009-05-07 | Jonathan Gordon Conn Veinot | Method for preparing nanocrystalline silicon in sio2 and freestanding silicon nanoparticles |
US8323731B2 (en) * | 2005-05-27 | 2012-12-04 | The Governors Of The University Of Alberta | Method for preparing nanocrystalline silicon in SiO2 and freestanding silicon nanoparticles |
US7390599B2 (en) * | 2005-10-11 | 2008-06-24 | Xerox Corporation | Silicon-containing overcoat layers |
US20070082207A1 (en) * | 2005-10-11 | 2007-04-12 | Xerox Corporation | Silicon-containing overcoat layers |
US8653217B2 (en) | 2007-05-01 | 2014-02-18 | Dow Corning Corporation | Method for forming anti-reflective coating |
US20120046486A1 (en) * | 2008-08-27 | 2012-02-23 | Evonik Goldschmidt Gmbh | PROCESS FOR PREPARING BRANCHED Si-H FUNCTIONAL POLYSILOXANES AND USE THEREOF FOR PREPARING LIQUID SiC- OR SiOC-LINKED, BRANCHED MODIFIED ORGANOMODIFIED POLYSILOXANES |
US8420748B2 (en) * | 2008-08-27 | 2013-04-16 | Evonik Goldschmidt Gmbh | Process for preparing branched Si-H functional polysiloxanes and use thereof for preparing liquid SiC- or SiOC-linked, branched modified organomodified polysiloxanes |
US20110236835A1 (en) * | 2008-12-10 | 2011-09-29 | Peng-Fei Fu | Silsesquioxane Resins |
US8809482B2 (en) | 2008-12-10 | 2014-08-19 | Dow Corning Corporation | Silsesquioxane resins |
Also Published As
Publication number | Publication date |
---|---|
DE69629405D1 (de) | 2003-09-18 |
DE69629405T2 (de) | 2004-06-09 |
KR100359392B1 (ko) | 2003-01-24 |
EP0725103A2 (de) | 1996-08-07 |
EP0725103B1 (de) | 2003-08-13 |
KR960031509A (ko) | 1996-09-17 |
EP0725103A3 (de) | 1997-07-16 |
JPH08208840A (ja) | 1996-08-13 |
TW413693B (en) | 2000-12-01 |
JP3542185B2 (ja) | 2004-07-14 |
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